Thermoplastic resin composition

ABSTRACT

A thermoplastic resin composition comprising a blend obtainable by blending 0.1 to 99% by weight of (a) a fluorine-containing polymer having a number-average molecular weight of 2000 to 1000000 and having hydroxy group or epoxy group at least at one of end portions of a main chain and side chain of the polymer, and 1 to 99.9% by weight of (b) a heat resisting thermoplastic resin having a crystalline melting point or glass transition temperature of not less than 150° C. The present invention can provide a composition comprising various heat resisting thermoplastic resins and a fluorine-containing polymer having a functional group which is capable of developing an affinity with said resins and forming a uniform dispersion.

TECHNICAL FIELD

The present invention relates to a thermoplastic resin composition whichcomprises a specific fluorine-containing polymer having a functionalgroup and a thermoplastic resin having a crystalline melting point orglass transition temperature of not less than 150° C., and has improvedmechanical and chemical properties.

BACKGROUND ARTS

Heat resisting crystalline thermoplastic resins (having a crystallinemelting point of not less than 150° C.) such as polyacetals, polyamides,aromatic polyesters, polyallylene-sulfides, polyketones, polyetherketones, polyamide imides and polyether nitrites are excellent inmechanical properties and moreover moldability, and therefore are usedfor functional parts for automobiles, industrial machineries, officeautomation equipments, and electrical and electronic equipments.Meanwhile there is a market demand for higher chemical resistance,sliding properties and the like, and particularly impact resistance isdesired to be enhanced because those resins are generally brittle. Also,heat resisting amorphous thermoplastic resins (having a glass transitiontemperature of hot less than 150° C.) such as polycarbonates,polyphenylene ethers, polyalylates, polysulphones, polyether sulphones,and polyetherimides are widely used for making the best use oftransparency, dimensional stability, impact resistance, and the like,but generally there are problems with chemical resistance, solventresistance and moldability.

Fluorine-containing resins such as polytetra-fluoroethylene (PTFE),tetrafluoroethylene/perfluoro-alkyl vinyl ether copolymer (PFA),tetrafluoroethylene/hexafluoropropylene copolymer (FEP), polyvinylidenefluoride (PVDF) and ethylene/tetrafluoroethylene copolymer (ETFE) areexcellent in thermal resistance, chemical resistance, solventresistance, weather resistance, sliding properties, pliability,electrical properties and the like, and are widely used for automobiles,industrial machineries, office automation equipments, electrical andelectronic equipments, and the like. However, there are many cases wherethose resins are inferior in mechanical properties and physical thermalresistance as represented by a deflection temperature under load, ascompared with heat resisting crystalline thermoplastic resins, and theuses thereof are within the limited range because the dimensionalstability is inferior as compared with heat resisting amorphousthermoplastic resins.

Attempts have been actively made to obtain novel materials by combininga fluorine-containing polymer (including resinous and elastomeric form)with the aforementioned heat resisting thermoplastic resins having nofluorine to modify such resins to eliminate disadvantages of the resins,and on the contrary by combining mainly a resinous fluorine-containingpolymer with the heat resisting thermoplastic resin having no fluorineto moldify such polymers.

First, as an example for simply melting and blending by the use of akneading machine, JP-A-202344/1982 discloses that a fluorine-containingelastomer commercially available is added to improve impact resistance,crack resistance and strength against thermal shock without imparingproperties of polyallylene sulfides such as thermal resistance, chemicalresistance, and the like. Also, JP-A-165647/1989 and JP-A-110156/1990disclose that a polymer, that is to say, a liquid crystal polymer(aromatic polyester or the like) forming an anisotropic melt is added todecrease a coefficient of linear expansion without impairing weatherresistance, chemical resistance, wear resistance and anti-soil propertyof a fluorine-containing polymer such as a PVDF and further to improvemechanical properties and moldability. As examples of a blend of aliquid crystal polymer and a PTFE, there are JP-B-5693/1992 andJP-A-230756/1988. JP-A-7850/1975 discloses that it is effective to blendthe PVDF for improving water absorption and hygroscopicity ofpolyamides.

Furthermore, JP-A-23448/1985 discloses an example that a property ofrelease from a mold is improved by blending a fluorine-containingpolymer with an aromatic polysulphone composition of which shrinkagefrom mold dimensions has been decreased by blending fibrousreinforcements such as glass fiber and wollastonite and inorganicfillers such as talc and glass beads.

Also, attempts have been widely and generally made to improve slidingproperties of various synthetic resins by blending a PTFE powder.

However, since a surface energy of a fluorine-containing polymer issmall, there is a problem that such a polymer is generally short of anaffinity with other materials. Therefore, when the fluorine-containingpolymer and other materials are melted and blended, there occurs a phaseseparation. Interfacial adhesion thereof is nearly nothingsubstantially, and an interfacial adhesive failure occurs easily, thefluorine-containing polymer is difficult to be dispersed in othermaterials during blending, and an aggregation occurs. Thus it isdifficult to display an effect of blending that polymer.

In order to eliminate such drawbacks and to enhance an affinity betweendifferent polymers, it is often conducted to add so-calledcompatibilizing agents as the third component. JP-A-218446/1987discloses a composition prepared by blending a thermoplasticfluorine-containing elastomer to improve impact resistance ofpolyallylene sulfides without imparing flowability thereof, and thatpatent publication describes that it is more effective to add afluoroaliphatic group-containing polymer to improve an affinity of thepolymer. Also, JP-A-62853/1988 discloses a method to add, as acompatibilizing agent, a graft polymer comprising a vinyl polymer havingepoxy group and a methyl methacrylate polymer or anacrylonitrile/styrene copolymer when blending polyallylene sulfides andthermoplastic resins containing a PVDF.

Also, claim 2 of the mentioned JP-A-165647/1986, JP-A-197551/1986 andJP-A-263144/1986 disclose that it is more effective to add an acrylicpolymer, polyvinyl acetate and polyvinyl methyl ketone, respectivelythan a simple blending, in blending a PVDF and a polymer forming ananisotropic melt.

JP-A-11109/1989 discloses an example of using, as a compatibilizingagent for blending polyamides and PVDF, a block polymer comprising anyone of N-vinylpyrrolidone or methyl(meta)acrylate and any one ofunsaturated ethylenic monomer, polycondensated monomer or lactam.

Also, JP-A-98650/1986 and JP-A-110550/1986 disclose that when blending apolyphenylene ether and a fluorine-containing polymer like a PVDF, acopolymer comprising polystyrene and an acrylic polymer is used as acompatibilizing agent, taking advantage of an excellent compatibility ofpolyphenylene ether with polystyrene and PVDF with acrylic polymer.

However, in JP-A-218446/1987, an effect of an improvement in affinityproperty is insufficient. It may be because a fluoroaliphatic group, inan compatibilizing agent is of low polymerization having carbon atoms ofnot less than 20. All the other publications substantially describes theexamples of using compatibilizing agents having no fluorine, which aresynthesized, making use of an excellent affinity between a PVDF and acarbonyl group-containing polymer such as acrylic polymer, and thefluorine-containing polymer is limited to the PVDF. In the method toimprove an affinity by the use of such a compatibilizing agent, there isa problem that physical properties of the molded articles deterioratebecause chemical resistance and thermal resistance of thecompatibilizing agents themselves are inferior to that of a maincomponent, i.e. the polymer.

Also, attempts have been made to improve dispersibility of a compositioncomprising a fluorine-containing polymer and a thermoplastic resin, by aso-called dynamic vulcanization. JP-A-185042/1991 discloses that, whenblending a crosslinkable fluorine-containing elastomer and athermoplastic polymer having a crystalline melting point or glasstransition temperature of not less than 150° C., the dispersibility isenhanced and a thermoplastic elastomer can be obtained by vulcanizingthe fluorine-containing elastomer during melting and blending.JP-A-172352/1991 also discloses that a fine dispersion of afluorine-containing rubber is achieved by improving impact resistance ofa polyphenylene sulfide by the use of a fluorine-containing elastomer byutilizing the dynamic vulcanization method.

Though those dynamic vulcanization methods are economically advantageoussince the vulcanization of the fluorine-containing elastomer is carriedout during melting and blending with other materials, there is a problemthat impurities resulting from vulcanizing agents and other additives,which are used in the usual vulcanization methods, remain in acomposition, and properties such as chemical resistance of a moldedarticle deteriorate.

On the other hand, there are reports on a composition using afluorine-containing polymer having a reactive functional group.JP-A-105062/1988, JP-A-254155/1988 and JP-A-264672/1988 discloseexamples of blending a matrix polymer and, for instance, afluoropolyether in which a functional group is introduced at the endthereof, a polymer containing a functional group and a polyfluoroalkylgroup having carbon atoms of 2 to 20 and a fluorine-containing elastomerhaving a functional group. However, any of those examples is a manner toform, a network structure by dispersing the polymer having two kinds offunctional groups in the matrix polymer and causing an inter-reactiontherebetween and to physically bond that network structure to the matrixpolymer, but not a manner to directly utilize a chemical affinity andreactivity with the matrix polymer.

Thus a combination of functional groups of not less than two kindsreacting with each other is necessary without fail, and also it isnecessary to provide the conditions for forming the network structure bythose functional groups. Also, a fluoropolyether is usually obtained asan oily substance and is expensive, and an effect of addition thereof isonly limited to an improvement of lubricity of the matrix polymer.Furthermore exemplified is only such a polyfluoroalkyl group-containingpolymer of a low molecular weight which is difficult to be prescribed asa polymer.

As mentioned hereinabove, when blending a fluorine-containing polymerand a thermoplastic resin, it is difficult to obtain a blend havingstable characteristics because the fluorine-containing polymer isgenerally short of an affinity, and physical properties of the moldedarticle obtained using that polymer are deteriorated. In order toimprove the affinity, various studies have been made in relation toadditives, but the present status is such that a composition comprisinga fluorine-containing polymer and a thermoplastic resin, which do notdeteriorate thermal resistance, chemical resistance and the like of thecomposition, has not yet been obtained.

The object of the present invention is to provide a compositioncomprising various heat resisting thermoplastic resins andfluorine-containing polymers having a functional group, which have agood affinity with the resins and are capable of forming uniformdispersing conditions.

DISCLOSURE OF THE INVENTION

The thermoplastic resin composition of the present invention comprises ablend obtainable by blending

(a) 0.1 to 99% (% by weight, hereinafter the same) of afluorine-containing polymer having a functional group and

(b) 1 to 99.9% of a heat resisting thermoplastic resin having acrystalline melting point or glass transition temperature of not lessthan 150° C.; said fluorine-containing polymer (a) having the functionalgroup is at least one selected from fluorine-containing polymers havingfunctional groups, in which a concentration of the functional groups atthe end portion of a main chain and the side chain portion is 2 to 2000μmol/g per the total weight of the fluorine-containing polymer,represented by the formula I!, ##STR1## wherein X is a structural unitof the formula --CH₂ CX¹ X²)-- (wherein X¹ and X² are the same ordifferent, and each is hydrogen atom, fluorine atom, --CH₂)_(p) (O)_(q)--R--B¹ (R is a dihydric hydrocarbon group having carbon atoms of 1 to20 or dihydric fluorine-substituted organic group having carbon atoms of1 to 20, B¹ is hydrogen atom, fluorine atom, hydroxy group or epoxygroup, p is 0 or 1 and q is 0 or 1), --OCO--R--B¹ (R and B¹ are the sameas above) or --COO--R--B¹ (R and B¹ are the same as above));

Y is a structural unit of the formula --(CF₂ CY¹ Y²)-- (wherein Y¹ andY² are the same or different, and each is hydrogen atom, fluorine atom,chlorine atom, --(CF₂)_(r) --(O)_(s) (R_(f))_(t) (CH₂)_(u) --B² (R_(f)is a dihydric fluorine-substituted organic group having carbon atoms of1 to 14, B² is hydrogen atom, halogen atom, hydroxy group, epoxy groupor glycidyloxy group, r is 0 or 1, s is 0 or 1, t is 0 or 1, and u is aninteger of 1 to 3) or --(CF₂)_(v) --B³ (B³ is hydrogen atom, fluorineatom or chlorine atom, v is an integer of 1 to 10));

both A¹ and A² are end portions of a main chain; provided that each of Xand Y may comprise two or more structural units;

Y may not be present when X has the structural unit derived from CH₂═CHF, CH₂ ═CF₂ or fluoroalkyl-α-substituted acrylate (substituent ishydrogen atom, fluorine atom or methyl);

X may not be present when Y has the structural unit derived from CF₂═CF₂ or CF₂ ═CFCl; at least one of A¹ and A² contains hydroxy group,epoxy group or glycidyl group when both of X and Y do not containhydroxy group, epoxy group or glycidyl group.

BRIEF EXPLANATION OF THE DRAWINGS

FIG. 1 is a microscopic photograph of a cut surface of the moldedarticle obtained in Example 2.

FIG. 2 is a microscopic photograph of a cut surface of the moldedarticle obtained in Example 3.

FIG. 3 is a microscopic photograph of a cut surface of the moldedarticle obtained in Comparative Example 1.

FIG. 4 is a microscopic photograph of a cut surface of the moldedarticle obtained in Comparative Example 2.

FIG. 5 is a stress-strain curve of the molded article obtained inExamples 6 to 8 and Comparative Examples 3 and 4.

FIG. 6 is a microscopic photograph of a cut surface of the moldedarticle obtained in Example 12.

FIG. 7 is a microscopic photograph of a cut surface of the moldedarticle obtained in Comparative Example 9.

PREFERRED EMBODIMENTS OF THE INVENTION

Though a prior resin composition of a heat resisting thermoplastic resinand a fluorine-containing polymer could provide a uniform molded articleonly by a special method, according to the present invention, there canbe provided a composition capable of easily making a uniform moldedarticle by introducing a specific functional group into afluorine-containing polymer.

The fluorine-containing polymer having a functional group is representedby the formula (I), and is characterized in that the polymer has hydroxygroup or epoxy group (inclusive of a glycidyl group) at least at one ofend portions of a main chain and end portions of side chains if present,and the fluorine-containing polymer (I) or a precursor polymer beforeintroducing a functional group to obtain (I) is prepared by a radicalpolymerization. The details are mentioned herein below.

The fluorine-containing polymer having a functional group of the presentinvention has basic structural units of X represented by --(CH₂ --CX¹X²)-- and Y represented by --(CF₂ --CY¹ Y²)--.

As monomers producing the structural unit X, there are employed, forinstance, olefins such as ethylene, propylene, 1-butane and isobutylene;for instance, fluoroalkenes such as CH₂ ═CHF, CH₂ ═CF₂, CH₂ ═C(CF₃)₂ andCH₂ ═CZ(CF₂)wZ (z is hydrogen atom or fluorine atom and w is an integerof 1 to 8. For instance, CH₂ ═CHCF₂ CF₂ CF₂ CF₃, CH₂ ═CHCF₂ CF₂ CF₂ CF₂CF₂ CF₃, CH₂ ═CFCF₃, CH₂ ═CFCF₂ CF₃, CH₂ ═CFCF₂ CF₂ CF₂ H and CH₂ ═CFCF₂CF₂ CF₂ CF₂ CF₂ H); alkylvinylethers, for instance, CH₂ ═CHOCH₂ CH₃, CH₂═CHOCH₂ CH₂ CH₂ CH₃ and ##STR2## fluoroalkyl vinylethers, for instance,CH₂ ═CHOCH₂ CF₂ CF₂ H, CH₂ ═CHOCH₂ CF₂ CF₂ CF₂ CF₂ H and CH₂ ═CHOCH₂ CH₂CF₂ CF₂ CF₂ CF₂ CF₂ CF₃ ; hydroxyalkyl vinylethers, for instance, CH₂═CHOCH₂ CH₂ CH₂ CH₂ OH; fluoroalkyl allylethers, for instance, CH₂═CHCH₂ OCH₂ CH₂ CF₂ CF₃ ; hydroxyalkyl allylethers, for instance, CH₂═CHCH₂ OCH₂ CH₂ OH; alkyl or allylvinyl esters, for instance, CH₂═CHOCOCH₃, CH₂ ═CHOCOC(CH₃)₃ and ##STR3## alkyl-α-substituted acrylates,of which substituent is hydrogen atom, fluorine atom or methyl, forinstance, CH₂ ═CHCOOCH₃, CH₂ ═C(CH₃)COOCH₃ and CH₂ ═CFCOOCH₃ ;fluoroalkyl-α-substituted acrylates, of which substituent is hydrogenatom, fluorine atom or methyl, for instance, CH₂ ═CHCOOCH₂ CF₂ CF₂ CF₃,CH₂ ═C(CH₃)COOCH₂ CF₂ CF₃, CH₂ ═C(CH₃)COOCH₂ CF₂ CF₂ H and CH₂ ═CFCOOCH₂CF₂ CF₃ ; hydroxy(fluoro)alkyl-α-substituted acrylates, of whichsubstituent is hydrogen atom, fluorine atom or methyl, for instance, CH₂═CHCOOCH₂ CH₂ OH, CH₂ ═C(CH₃)COOCH₂ CH₂ OH and CH₂ ═C(CH₃)COOCH₂ CF₂ CF₂CH₂ OH; CH₂ ═CHCH₂ C(CF₃)₂ OH; CH₂ ═CHCH₂ OH; ##STR4##

As monomers producing the structural unit Y, there are employed, forinstance, fluoroalkenes such as CF₂ ═CFH, CF₂ ═CF₂, CF₂ ═CFCl, CF₂═CZ(CF₂)_(w) Z (Z and w are the same as those mentioned hereinbefore,for instance, CF₂ ═CHCF₃, CF₂ ═CFCF₃, CF₂ ═CFCF₂ CF₃ and CF₂ ═CFCF₂ CF₂H); formulae, for instance, CF₂ ═CFCH₂ CH₂ OH, CF₂ ═CFCF₂ CH₂ OH, CF₂═CFCF₂ CF₂ CH₂ CH₂ OH and ##STR5## a compound represented by CF₂═CF--R_(f) --(CH₂)_(x) --B² (R_(f) and B₂ are the same as mentionedhereinabove, and x is an integer of 1 to 3); perfluoro(alkylvinylether), for instance, CF₂ ═CFOCF₃, CF₂ ═CFO(CF₂ CF(CF₃)O)_(y) CF₂ CF₂CF₃ (y is an integer of 1 to 3), and CF₂ ═CFOCF₂ CF₂ CF₂ CF₃ ; formulae,for instance, CF₂ ═CFOCF₂ CF₂ CH₂ OH, CF₂ ═CFOCF₂ CF₂ CF₂ CH₂ OH, CF₂═CFOCF₂ CF(CF₃)OCF₂ CF₂ CF₂ CH₂ OH, CF₂ ═CFOCF₂ CF₂ CH₂ Br, CF₂ ═CFOCF₂CF₂ CH₂ OCF₂ CF₂ CH₂ F, CF₂ ═CFOCF₂ CF₂ CH₂ I and CF₂ ═CFOCF₂CF(CF₃)OCF₂ CF₂ CH₂ I: a compound represented by CF₂ ═CF--O--R_(f)--(CH₂)_(z) --B² (R_(f) and B² are the same as mentioned hereinabove,and z is an integer of 1 to 3); perfluoro(alkylallylether), forinstance, CF₂ ═CFCF₂ OCF₂ CF₂ CF₃.

The structural units X and Y each may comprise two kinds or more ofstructural units, Y may not be present, when X has the structural unitderived from CH₂ ═CHF, CH₂ ═CF₂ or fluoroalkyl-α-substituted acrylates(A substituent is hydrogen atom, fluorine atom or methyl). X may not bepresent, when Y has the structural unit derived from CF₂ ═CF₂ or CF₂═CFCl.

A¹ and A² representing the end portions of a main chain-X-Y- are cutpieces of an initiator or a chain transfer agent, for instance, --OCOR¹,--OR¹, --R¹, COOH, hydrogen atom, halogen atom (R¹ is an alkyl group orfluoroalkyl group having carbon atoms of 1 to 10), but not limited tothose. When any of structural units X and Y does not include astructural unit having hydroxy group, epoxy group or glycidyl group, atleast one of A¹ and A² must include hydroxy group, epoxy group orglycidyl group.

A basic component of a fluorine-containing polymer (a) having afunctional group has the structure represented by the formula (I), andis formed by a radical polymerization. As is explicit from the formula(I), the polymer does not have an ether bond at a portion of the mainchain. A fluorine-containing polymer having an ether bond at the bondedportion of the main chain, for instance, a perfluoroxy alkylene unit isalso disclosed in JP-B-42446/1991 besides the JP-A-105062/1988,JP-A-254155/1988 and JP-A-264672/1988. That fluoropolyether is usuallymade by an ion polymerization, and is expensive. Furthermore, thefluoropolyether of a high molecular weight is difficult to be obtained.The fluoropolyether becomes in the form of grease or oil at roomtemperature or at a high temperature, and it is difficult to form auniform blend of fluoropolyether alone with a thermoplastic resin, whichresults in deterioration of physical properties of the obtained blend.Also, it is difficult to introduce a side chain into thefluoropolyether.

A functional group (hydroxy group or epoxy group (Glycidyl group is alsoincluded therein, hereinafter the same)) in the fluorine-containingpolymer represented by the formula (I) can be made also by using thementioned functional group-containing monomer, and also can beintroduced, for example, by the method mentioned below.

For instance, there is a method (method with an initiator) to polymerizea basic component by the use of an initiator for the radicalpolymerization, which has a functional group to be introduced. Whenusing, for instance, a hydroperoxide as an initiator, hydroxy group canbe introduced at the end of the main chain.

Also, a functional group can be introduced by the use of a specificchain transfer agents (method with a chain transfer agent). Hydroxygroup is introduced at the end of the main chain when, for instance,methanol and mercaptoethanol are used as a chain transfer agent.

Also, another preferable method is the one (polymer reaction method) tointroduce a functional group at the end or side chain of a polymer by apolymer reaction after polymerization. The polymer reaction methodincludes a polymerization using a radical polymerization initiator,which can easily convert a cut piece of the initiator at the end of thepolymer into an intended functional group after polymerization and, inthe same manner, a polymerization using a chain transfer agent andcomonomer, which can easily convert the ends of a main chain and sidechain of the polymer into an intended functional group afterpolymerization.

As a polymer reaction method, there is an example, for instance, toconvert, into an intended functional group, iodine at the end of apolymer polymerized by using, as a chain transfer agent, an iodinatedcompound containing an iodine, such as a fluorine-containing elastomerand a thermoplastic fluorine-containing elastomer. Concretely, suitableis a fluorine-containing elastomer disclosed in JP-A-40543/1977, whichis mainly comprises a copolymer comprising a VDF and at least one kindof the other fluorine-containing monomers which are copolymerizable withthe VDF, wherein 0.001 to 10% by weight, preferably 0.01 to 5% by weightof iodine is bonded at the end of a polymer chain, and a thermoplasticfluorine-containing elastomer disclosed in JP-B-4728/1982, which has atleast one block of fluorine-containing resin as a hard segment and atleast one block of fluorine-containing elastomer as a soft segment,wherein the thermoplastic fluorine-containing elastomer is a linear,branched or radial block copolymer having a weight ratio offluorine-containing resin to fluorine-containing elastomer of 5:95 to60:40. An iodine of a fluorine-containing polymer, of which end isiodinated, has much reactivity and can be converted to a functionalgroup such as epoxy group, hydroxy group, carboxyl group, amino groupand isocyanate group by the known organic chemical method. The end ofthe polymer becomes an epoxy group after addition of an allylalcohol andthen dehydroiodination by an alkali, or becomes hydroxy group by addingethylene and further reacting with dimethyl sulfoxide.

Also, as disclosed in JP-A-12734/1987, a side chain typefluorine-containing polymer having a functional group can be made byletting a halogen be contained in the side chain by copolymerizing 0.05to 20% by mole of a halogen-containing monomer among those representedby the formula of CF₂ ═CFO--(CF₂ CFR² O)_(a) --(CF₂ CF₂ CH₂ O)_(b) --CF₂CF₂ --CH₂ --R³ (wherein R² is F or CF₃, a is an integer of 0 to 2, b isan integer of 0 to 2 and R³ is a halogen atom), in which R³ is selectedfrom Cl, Br and I, and 80 to 99.95% by mole of a monomer producing astructural unit X and a structural unit Y if necessary, and then byconverting to a functional group in the same manner as the example ofthe iodine terminated fluorine-containing polymer.

As a method to introduce a functional group by using a polymer reaction,there can be adopted, for instance, as shown in Polym. Mater. Sci Eng.,49,518 (1983), such a method as to add a nucleophilic functional groupinto a double bond produced by dehydrofluorinating a fluorine-containingelastomer having vinylidene fluoride with a base. However, that methodhas a drawback that the functional group is difficult to bequantitatively introduced.

It is naturally possible to further convert the fluorine-containingpolymer having a functional group which is introduced by each of thementioned methods, to the polymer having the desired functional group byapplying the usual organic chemical technique to the polymer reaction.For instance, the iodine at the end and/or side chain of thefluorine-containing polymer can also be converted to glycidyloxy groupby converting the iodine of the polymer to hydroxy group and furtherreacting with an epichlorohydrin.

Also, it is possible to combine the functional group introducing methodssuch as the method with an initiator, method with a chain transferagent, copolymerization method and polymer reaction method. The reactionfor introducing a functional group can also be carried out in a meltingand kneading equipment such as an extruder, and not limited to in apolymerization reactor for a general use.

In the formula (I), such a polymer as containing CH₂ unit in a mainchain in combination of X and Y as mentioned below is preferable becausea wide range of temperature for kneading with a thermoplastic resin canbe selected and a compatibility with the thermoplastic resin isrelatively excellent among fluorine-containing polymers.

That is to say, one (referred to as Polymer P¹) is a polymer using CH₂═CF₂ (vinylidene fluoride: VDF) as at least one component of X in theformula (I) (others are the same as those of the formula (I)), andanother one (referred to as Polymer P²) is a copolymer containing atleast one of hydrocarbon olefins as X (VDF is not contained) and atleast one of CF₂ ═CF₂ (tetrafluoroethylene: TFE), CF₂ ═CFCl(chlorotrifluoro-ethylene: CTFE) or CF₂ ═CFCF₃ (hexafluoropropene: HFP)as Y (others are the same as those of the formula (I)). Any of thosepolymers has hydroxy group or epoxy group at least at one of the mainchain and the end of the side chain thereof.

Among those polymers having CH₂ unit at the main chain, furtherpreferable is the one which is excellent in a thermal stability (thermalresistance), when kneaded with a thermoplastic resin. The main chain andthe end of the side chain, which have a functional group, are usuallyinferior to the other parts in thermal resistance, and it is unavoidableeven if there is a thermal decomposition to a certain extent on kneadingas far as an effect thereof can be recognized. However, at least mainportions of the main chain and the side chain of the aforesaidfluorine-containing polymer having a functional group should havethermal resistance of 170° C. at lowest, preferably not less than 250°C. The thermal resistance depends mainly on a kind and ratio ofcomponents of the monomers to be used. In the Polymer P¹ and Polymer P²,when a hydrocarbon olefin is used as X, it is recommendable to lower aratio of the hydrocarbon olefins such as alkylvinyl ether and alkylvinylester excluding CH₂ ═CH₂, CH₂ ═CHCH₃ and CH₂ ═C(CH₃)₂ in the polymer tonot more than 20% by mole. This is because those may be thermally themost unstable portions, among the monomers producing thefluorine-containing polymer having a functional group of the presentinvention.

The thermal resistance of the present invention means a temperature atthe time of weight decrease by 1% in a measurement (raising at a rate of10° C./minute) of a thermobalance in a nitrogen gas stream.

Among the Polymer P¹ and Polymer P², there are employed belowparticularly preferable fluorine-containing polymers having a functionalgroup in order to further give the features such as oil resistance andchemical resistance, which are inherent to fluorine-containing polymers,to the composition, even if the thermal resistance is enough asmentioned hereinabove.

That is to say, the Polymer P¹ essentially comprises a polyvinylidenefluoride (PVDF) and VDF, and is obtained by copolymerization with atleast one selected from, for instance, TFE, CTFE, perfluoro(alkylvinylether), perfluoro(alkylallyl ether), CH₂ ═C(CF₃)₂, CF₂ ═CZ(CF₂)_(w) Z (Zand w are the same as mentioned hereinabove), CH₂ ═CZ(CF₂)_(w) Z (Z andw are the same as mentioned hereinabove), CF₂ ═CFR_(f) (CH₂)_(x) --B₂and fluorine-containing olefins such as fluoroalkene represented by CF₂═CFOR_(f) (CH₂)_(z) --B² (R_(f), B², x and z are the same as mentionedhereinabove), and occasionally furthermore with at least one hydrocarbonolefin selected from CH₂ ═CH₂, CH₂ ═CHCH₃ and CH₂ ═C(CH₃)₂, wherein atleast one end of the main chain and the side chains of the polymer hashydroxy group or epoxy group.

The Polymer P² is a polymer containing at least one hydrocarbon olefinselected from CH₂ ═CH₂, CH₂ ═CHCH₃ and CH₂ ═C(CH₃)₂, at least one ofTFE, CTFE, and CF₂ ═CFCF₃ (hexafluoropropene: HFP), and occasionally,further at least one fluorine-containing olefin selected from, forinstance, perfluoro(alkylvinyl ether), perfluoro(alkylallyl ether), CH₂═C(CF₃)₂, CF₂ ═CZ(CF₂)_(w) Z (Z and w are the same as mentionedhereinabove), CH₂ ═CZ(CF₂)_(w) Z (Z and w are the same as mentionedhereinabove), fluoroalkylvinylether, CF₂ ═CFR_(f) (CH₂)_(x) --B² andfluoroalkene represented by CF₂ ═CFOR_(f) (CH₂)_(z) --B² (R_(f), B², xand z are the same as mentioned hereinabove), wherein at least one endof the main chain and the side chains of the polymer has hydroxy groupor epoxy group.

A molecular weight of the fluorine-containing polymer having afunctional group of the present invention is the same level as those ofa usual fluorine-containing resin and fluorine-containing elastomerexcept a PTFE which is said to have a high molecular weight of usuallynot less than millions, and is 2000 to 1000000 in a number-averagemolecular weight. When the molecular weight is too low, thermalresistance and chemical resistance are impaired, and therefore, it isnecessary to decrease a content of a fluorine-containing polymer havinga functional group in the composition. When the molecular weight is toohigh, moldability is impaired. Preferable number-average molecularweight differs depending on a kind of a thermoplastic resin and apurpose of the composition, but is about 10000 to 500000. Aconcentration of functional groups in the fluorine-containing polymer ofthe present invention may be a minimum necessary for improving adispersion condition when blending with the thermoplastic resin. Whenthe functional group is only at the end of a molecule, the concentrationof the functional group is too low and the effect is insufficient unlessthe fluorine-containing polymer is of relatively low molecular weight.In case where a functional group is introduced at the side chain with afunctional group-containing comonomer or by a high polymer reaction, theconcentration of the functional group can be relatively freely selectedirrespective of a molecular weight. However, an excessive concentrationof the functional group is not desirable by the reason of a restrictionin the production and in view of properties such as thermal resistanceand chemical resistance of the composition. The concentration of thefunctional groups both at the ends and in side chains of the moleculecan be 2 to 2000 μmol/g, particularly preferably 2 to 1000 μmol/g perthe total weight of the fluorine-containing polymer.

The fluorine-containing polymer (a) having a functional group of thepresent invention may be in either resinous or elastomeric formdepending on a kind of a monomer to be used and a ratio of componentsthereof. The resin is discriminated from the elastomer in a point thatthe latter has a glass transition temperature lower than roomtemperature, and either one can be selected depending on the purpose ofa blend. The elastomeric fluorine-containing polymer having a functionalgroup is used for the purposes to improve impact resistance of thethermoplastic resin and to obtain a blend in the elastomeric form.

In the present invention, the fluorine-containing polymer (a) having afunctional group is blended with a thermoplastic resin (b) of acrystalline melting point or a glass transition temperature of not lessthan 150° C . As the thermoplastic resin (b), there are, for example,polyacetals, polyamides, polycarbonates, polyphenylene ethers, aromaticpolyesters, aromatic polyesteramides, aromatic azomethines, polyallylenesulfides, polysulfones, polyether sulfones, polyketones, polyetherketones, polyetherimides, polyamide imides, polymethyl pentenes andpolyether nitriles. Among those, preferable for the present inventionare thermoplastic resins which have a high thermal resistance, and donot deteriorate thermal resistance of a composition after mixed with thefluorine-containing polymer (a) having a functional group, orthermoplastic resins, for which usual impact modifiers and chemicalresistance modifiers cannot be used because thermal resistance isdeteriorated thereby. Examples of such resins are aromatic polyesters,polyamides, polyamide imides, polyallylene sulfides, polyketones,polyether nitriles, polycarbonates, polyphenylene ethers, polysulfones,polyetherimides and polyimides.

Further, particularly preferable are, for example, polyallylenesulfides, of which impact resistance is generally desired to be improvedwithout impairing thermal resistance and chemical resistance, andpolyamides which are desired to improve solvent resistance, particularlygasohol resistance for the use as materials for auto parts and aromaticpolyesters which are expected to enhance moldability and mechanicalproperties of the fluorine- containing polymer, being added thereto.Among those, particularly preferable are liquid crystal polyestersforming an anisotropic melt, which can be expected to enhance, to alarge extent, mechanical properties, moldability, dimensional stabilityand deflection temperature under load by enhancing a compatibility withthe fluorine-containing polymer, because those polyesters have highmodulus of elasticity and are excellent in moldability and dimensionalstability.

Also, when considering reactivity of the fluorine-containing polymer (a)having a functional group of the present invention and a thermoplasticresin (b), since polyphenylene sulfides contain mercapto group,polyamides contain carboxyl group and amino group, and aromaticpolyesters contain hydroxy group, carboxyl group and ester group, thereis a high possibility of those resins' reacting with hydroxy group orepoxy group (also inclusive of glycidyl group) in thefluorine-containing polymer having a functional group of the presentinvention. From this point of view, too, those resins are preferable.

The functional group of the fluorine-containing polymer of the presentinvention are epoxy group (including glycidyl group) and hydroxy group.The reactivity of those functional groups is high with an ester bond ofa main chain and hydroxy group and carboxyl group at the end when theheat resisting thermoplastic resin (b) is an aromatic polyester, with anamide bond of main chain and carboxyl group and amino group at the endwhen the resin is a polyamide (PA), and with mercapto group at the endwhen the resin is a polyallylene sulfide. That is to say, it can bethought that those highly reactive functional groups are introduced inthe fluorine-containing polymer, and partly react with the main chain orthe end of the thermoplastic resin to improve a compatibility of thepolymer or that the introduction of the functional group enhances apolarity of the fluorine-containing polymer, which improves an interfaceaffinity with the thermoplastic resin and a dispersibility withoutparticularly causing a chemical reaction. Also, it can be consideredthat a part of the thermoplastic resin causes a chemical reaction withthe fluorine-containing polymer and the reaction products act as acompatibilizing agent.

Therefore, in the composition of the present invention, a blend of thefluorine-containing polymer (a) having the functional group and thethermoplastic resin (b) is presumed to be present in the form of

(1) a mere mixture of the fluorine-containing polymer (a) having thefunctional group and the thermoplastic resin (b),

(2) a reaction product between the fluorine-containing polymer (a)having the functional group and the thermoplastic resin (b) or

(3) a mixture of (1) and (2).

Thus, though a mechanism of the blend is not clear, it does not limitthe present invention.

It is not excluded from the present invention that the thermoplasticresin (b) is modified by a normal method in order to enhance an affinityor reactivity with the fluorine-containing polymer having a functionalgroup of the present invention.

The resin composition of the present invention can also contain polymercomponents other than the thermoplastic resin (b) and thefluorine-containing polymer (a) having a functional group.

Preferable components are fluorine-containing polymers which haveneither hydroxy group nor epoxy group at the main chain and the end ofthe side chain in the formula (I). Particularly preferable are

(1) a perfluoro fluorine-containing resin or elastomer such as PTFE(including a copolymer having less than 1% by weight offluorine-containing olefin copolymerable with TFE),TFE/perfluoro(alkylvinyl ether) copolymer (so-called PFA), TFE/HFPcopolymer (so-called FEP) and TFE/perfluoro(alkylvinyl ether)/HFPterpolymer;

(2) a resinous copolymer, in which a mole ratio of an ethylene to a TFEand/or CTFE, which are known as a so-called ETFE and ECTFE, is 2:3 to3:2 and the third fluorine-containing monomer copolymerable therewith iscontained in an amount of 0 to 15% by mole per a total amount of theethylene and the TFE and/or CTFE monomer, or an elastomeric copolymerhaving about 40 to 90% by mole of ethylene, about 0.1 to 20% by mole ofTFE and/or CTFE and about 10 to 60% by mole of the thirdfluorine-containing monomer. As the third fluorine-containing monomer,there is used at least one of those represented by CH₂ ═CZ(CF₂)_(w) Z,CF₂ ═CZ(CF₂)_(w) Z, CF₂ ═CFO(CF₂)_(w) Z (Z and w are the same asmentioned hereinabove) and CH₂ ═C(CF₃)₂ ;

(3) a PVDF and a VDF copolymer (a resinous or elastomeric copolymer ofthe VDF and at least one fluorine-containing olefin selected from TFE,CTFE, HFP, CH₂ ═C(CF₃)₂, (CF₃)₂ C═O, and the like), wherein VDF/HFPcopolymer, VDF/CTFE copolymer and VDF/TFE/HFP or CTFE terpolymer usuallybecome an elastomer in the range of about 20 to 80 % by mole of VDF,less than about 40% by mole of TFE, about 10 to 60% by mole of HFP andabout 15 to 40% by mole of CTFE; and

(4) other fluorine-containing resins or elastomers such aschlorotrifluoroethylene (PCTFE) and poly(fluoroalkyl-α-substitutedacrylate) (a substituent is hydrogen atom, a methyl, fluorine atom orchlorine atom).

That is to say, in the compositions having three components of theaforesaid fluorine-containing polymer (a) having a functional group, thethermoplastic resin (b) and the fluorine-containing polymer having nofunctional group, it can be thought that a mixture of a part of thethermoplastic resin (b) in the composition and the fluorine-containingpolymer (a) having a functional group functions as a compatibilizingagent and enhances a dispersibility, and a mechanical property, chemicalresistance, and the like, which cannot be obtained in case of a simpleblend of a fluorine-containing polymer having no functional group and athermoplastic resin (b), can be enhanced.

Therefore, in those compositions, it is preferable that thefluorine-containing polymer (a) having a functional group and thefluorine-containing polymer having no functional group are highlycompatible with each other.

For example, when mixing the perfluoro fluorine-containing resin orelastomer of (1) above and the polymer of (2) above, such as a ETFE andECTFE, with the thermoplastic resin, it is the most preferable to mix afluorine-containing polymer having a functional group, which has thefunctional group at the end or the side chain and has a structuresimilar to those of fluorine-containing polymers to be mixed therewith.

Also, when mixing the PVdF or the VdF copolymer of (3) above with thethermoplastic resin, it is the most preferable to mix thefluorine-containing polymer having a functional group, which is selectedfrom PVdF and VdF copolymers and has the functional group at the end orthe side chain thereof.

It is necessary to blend the thermoplastic resin (b) and thefluorine-containing polymer (a) having a functional group or to blendthose and a fluorine-containing polymer having no functional group undermelting and fluidizing conditions at least at not less than acrystalline melting point or a glass transition temperature of thethermoplastic resin. It is desirable that the fluorine-containingpolymer having a functional group is also under melting conditionsduring blending, but a non-melting property may be maintained because ofa high melting viscosity or a crosslinking property.

The resin composition of the present invention has the functional groupat the end of the main chain and/or the side chain, and is obtained bymixing a fluorine-containing polymer (a) having a molecular weight of2000 to 1000000 and a thermoplastic resin (b) having a crystallinemelting point or glass transition temperature of not less than 150° C .The polymer (a) is 0.1 to 99% by weight, and the resin (b) is 1 to 99.9%by weight.

When (a) is 0.1 to 40% by weight and (b) is 60 to 99.9% by weight, suchproperties as an impact resistance, sliding property, chemicalresistance and moldability can be improved by a fluorine-containingpolymer, though those properties are drawbacks for many of thermoplasticresins. Also, when (a) is 40 to 99% by weight and (b) is 1 to 60% byweight, a strength, deflection temperature under load, moldability anddimensional stability of the fluorine-containing polymer can be improvedby the thermoplastic resin. When, in a weight ratio to the resincomposition, (a) is less than 0.1% by weight and (b) is less than 1% byweight, the effect of that improvement becomes unsatisfactory.

A content, in the composition, of a fluorine-containing polymer having afunctional group and a kind thereof differ depending on a kind,position, concentration, basic component and molecular weight of thefunctional group, and therefore, cannot be determined unequivocally butis selected depending on a kind of thermoplastic resin to be blended inthe mentioned range and a purpose of blending.

The preferable resin composition of the present invention is thecomposition comprising a fluorine-containing polymer having hydroxygroup or epoxy group at the end of main chain or the side chain and apolyallylene sulfide, polyamide, aromatic polyester or polycarbonate.

A polyallylene sulfide is excellent in thermal resistance, chemicalresistance, and mechanical properties, but inferior in impactresistance.

There can be obtained a composition, of which impact resistance isimproved by mixing a fluorine-containing elastomer particularly having anumber-average molecular weight of 2000 to 200000, amongfluorine-containing polymers (a) having a functional group.

As a functional group of the fluorine-containing elastomer having afunctional group, there are employed hydroxy group and epoxy group(including glycidyl group). Either of those groups enhances adispersibility and impact resistance.

A preferable concentration of the functional group differs depending ona kind and mixing ratio of a fluorine-containing elastomer and apolyallylene sulfide, and 2 to 2000 μmol/g, particularly 2 to 1000μmol/g is sufficiently effective per a total amount of thefluorine-containing elastomer.

As the aforesaid fluorine-containing elastomers having a functionalgroup, there can be used those, in which the functional groups areintroduced at the respective ends or side chains thereof, such asvinylidene fluoride-hexafluoropropylene copolymer, vinylidenefluoride-tetrafluoroethylene-hexafluoro-propylene copolymer, vinylidenefluoride-chlorotrifluoroethylene copolymer,vinylidenefluoride-tetrafluoroethylene-chlorotrifluoroethylenecopolymer, propylene-tetrafluoroethylene copolymer,tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer,tetrafluoroethylene-vinylidene fluoride-propylene copolymer,ethylene-tetrafluoroethylene-hexafluoropropylene copolymer,ethylene-hexafluoropropylene copolymer, perfluoroalkyl acrylateelastomer, tetrafluoroethylene-alkylvinylether copolymer, andtetrafluoroethylene-alkylvinylester copolymer. Among those, particularlypreferable are vinylidene fluoride-hexafluoropropylene copolymer,vinylidene fluoride-tetrafluoroethylene-hexafluoro-propylene copolymerand propylene-tetrafluoroethylene copolymer, in which hydroxy group orepoxy group (including glycidyl group) is introduced respectively.

The fluorine-containing elastomer having a functional group and thepolyallylene sulfide can be used in the range of 0.1 to 40% by weightand 60 to 99.9% by weight, respectively, particularly preferably 5 to30% by weight and 70 to 90% by weight, respectively.

When the fluorine-containing elastomer having a functional group is lessthan 5% by weight, impact resistance cannot be improved sufficiently,and contrarily when exceeding 30% by weight, mechanical strengthdecreases remarkably.

Perfluoro fluorine-containing resins (PTFE, FEP, PFA, and the like),ETFE, ECTFE, PVdF and VDF copolymer resins are excellent in thermalresistance, chemical resistance, weather resistance, electricalproperties, and the like, but there are many cases where those resinsare inferior to the heat resisting crystalline thermoplastic resin (b)in mechanical properties and physical thermal resistance as representedby a deflection temperature under load.

The mechanical property and deflection temperature under load, whichfluorine-containing resins themselves have, can be improved, instead ofusing the aforesaid fluorine-containing resins, by blending an aromaticpolyester or polycarbonate with the fluorine-containing resin having afunctional group of the present invention, which is introduced at theend or the side chain thereof, or by using, as a compatibilizing agent,the fluorine-containing polymer having a functional group of the presentinvention, for the mentioned blend of the fluorine-containing resin andthe aromatic polyester or polycarbonate.

When blending with the aromatic polyester or polycarbonate, the both ofhydroxy group and epoxy group (including glycidyl group) of the presentinvention can be used as the functional group of the fluorine-containingpolymer having the functional group. It is more preferable to use thefluorine-containing polymer having hydroxy group at the end or sidechain thereof, which is considered to easily cause antransesterification with an ester bond or carbonate bond in the mainchain of the aromatic polyester or polycarbonate.

A preferable concentration of the functional group differs depending onthe kind of the fluorine-containing polymer and the kind and ratio ofthe aromatic polyester or polycarbonate, and 2 to 2000 μmol/g,particularly 2 to 1000 μmol/g is sufficiently effective per a totalweight of the fluorine-containing polymer having a functional group.

When blending two components of the fluorine-containing resin having afunctional group and the aromatic polyester or polycarbonate, variousfluorine-containing resins having a functional group can be selected,and those having hydroxy group at the end or side chain thereof, such asPTFE, FEP, PFA, ETFE, ECTFE, PVdF, and VDF-TFE copolymer are preferable.Mechanical properties and deflection temperature under load, which eachof the corresponding fluorine-containing resins themselves has, can beimproved.

In case of a blend composition by blending the fluorine-containingpolymer having a functional group of the present invention as acompatibilizing agent with a blend of the fluorine-containing resin andthe aromatic polyester or polycarbonate, various combinations can beused. Most preferable are those such as a composition obtainable byblending a mixture of perfluoro fluorine-containing resin (PTFE, FEP,PFA, and the like) and aromatic polyester or polycarbonate, wherein eachof the corresponding perfluoro fluorine-containing resins, in whichhydroxy group is introduced at the end or side chain thereof, is blendedas a compatibilizing agent, a composition obtainable by blending amixture of a ETFE (or ECTFE) and an aromatic polyester or polycarbonatewith ethylene/tetrafluoroethylene copolymer (orethylene/chlorotrifluoroethylene copolymer), in which hydroxy group isintroduced at the end or side chain thereof, and a compositionobtainable by blending a mixture of a PVDF and an aromatic polyester orpolycarbonate with a fluorine-containing polymer selected from a PVDF orVDF copolymer, in which hydroxy group is introduced at the end or sidechain thereof.

In those cases, a content of the fluorine-containing polymer having afunctional group, as a compatibilizing agent effective for enhancing adispersibility, is 0.5 to 30% by weight, preferably 1 to 15% by weightper a total weight of the composition.

Also, by melting and blending an aromatic polyester with particularly afluorine-containing elastomer having hydroxy group, among thefluorine-containing polymers having a functional group, there occurspartially a chemical reaction (transesterification and the like), and athermoplastic elastomer composition can be obtained. Also, thermoplasticelastomers having various hardnesses can be obtained by melting andblending the fluorine-containing elastomer having hydroxy group and thearomatic polyester at an optionally selected blending ratio. Apreferable concentration of a functional group differs depending on thekinds, blending ratio, and the like of the fluorine-containing elastomerand the aromatic polyester or polycarbonate, but is 2 to 2000 μmol/g,particularly preferably 2 to 1000 μmol/g per total weight of thefluorine-containing elastomer.

In that case, as the fluorine-containing elastomer having hydroxy group,there can be used a vinylidene fluoride-hexafluoropropylene copolymer,vinylidene fluoride-tetrafluoroethylene-hexafluoro-propylene copolymer,vinylidene fluoride-chloro-trifluoroethylene copolymer, vinylidenefluoride-tetrafluoroethylene-chlorotrifluoroethylene copolymer,propylene-tetrafluoroethylene copolymer,tetrafluoro-ethylene-perfluoroalkyl vinyl ether copolymer,tetrafluoroethylene-vinyliden fluoride-propylene copolymer,ethylene-tetrafluoroethylene-hexafluoro-propylene copolymer,ethylene-hexafluoropropylene copolymer, perfluoroalkyl acrylateelastomer, tetrafluoroethylene-alkylvinyl ether copolymer andtetrafluoroethylene-alkylvinyl ester copolymer, in which hydroxy groupis introduced at the end or side chain thereof. Among those,particularly preferable are vinylidene fluoride-hexafluoropropylenecopolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoro-propylenecopolymer and propylene-tetrafluoroethylene copolymer, in which hydroxygroup is introduced at the respective ends or side chains thereof.

In that thermoplastic elastomer composition, a weight ratio of thefluorine-containing elastomer having hydroxy group can be 50 to 99.9% byweight, and that of the aromatic polyester or polycarbonate, 0.1 to 50%by weight. In order to provide a high temperature flowability as thethermoplastic resin together with an elasticity as the elastomer,particularly preferable is 70 to 98% by weight of thefluorine-containing elastomer having hydroxy group and 2 to 30% byweight of the aromatic polyester or polycarbonate.

The modifying composition and the thermoplastic elastomer composition ofthe fluorine-containing polymer mentioned hereinabove can be used.

As the aromatic polyester, there are employed, for example, a condensateof dibasic acids such as adipic acid, terephthalic acid,2,6-naphthalene-dicarboxylic acid and 4,4'-biphenil carboxylic acid, anddihydric alcohols such as ethylene glycol, trimethylene glycol,tetramethylene glycol, pentamethylene glycol, hexamethylene glycol,1,4-cyclohexanedimethanol and bisphenol A (for instance, polyethyleneterephthalate, polybutylene terephthalate, poly 1,4-cyclohexanedimethylene terephthalate, poly 2,2-propanebis(4-phenyltere/isophthalate)!); an aromatic polyester (liquid crystalcopolyester) forming an anisotropic melt phase, and the like.

Among those, it is preferable to use a liquid crystal copolyester havinga high strength because of an orientation thereof and showing a highflowability on melting. As the liquid crystal copolyesters, there areemployed those comprising, for example one or more of aromaticdicarboxylic acid and alicyclic dicarboxylic acid; one or more ofaromatic diol, alicyclic diol and aliphatic diol; one or more ofaromatic hydroxycarboxylic acids. Typical combinations are, forinstance, the one having main components of p-hydroxybenzoic acid,biphenildiol and terephthalic acid (for example, Econol E2000 and E6000available from Sumitomo Chemical Industries, Co., Ltd., Xydar RC/FC400and 300 available from Nippon Petrochemicals Co., Ltd., Vectra C seriesavailable from Polyplastics Co., Ltd., UENO LCP2000 available from UenoFine Chemicals Industry Ltd. and Idemitsu LCP300 available from IdemitsuPetrochemical Co., Ltd.); the one having main components ofp-hydroxybenzoic acid and 6-hydroxynaphthoic acid (for example, VICTREXSRP available from ICI Japan Ltd., UENO LCP1000 available from Ueno FineChemicals Industry Ltd., Vectra A series available from PolyplasticsCo., Ltd., Novaculate E324 available from Mitsubishi Kasei Corp.,Idemitsu LCP300 available from Idemitsu Petrochemical Co., Ltd. andRodrun LC-5000 available from Unitika Ltd.); the one having maincomponents of p-hydroxybenzoic acid, terephthalic acid and aliphaticdiol (for example, Novaculate E310 available from Mitsubishi KaseiCorp., Idemitsu LCP100 available from Idemitsu Petrochemical Co., Ltd.,Rodrun LC-3000 of Unitika Ltd., and X7G available from Eastman KodakCo.).

When blending these liquid crystal copolyesters and thefluorine-containing elastomer having a functional group of the presentinvention, in consideration of thermal resistance of thefluorine-containing elastomer having a functional group, preferable arecopolyesters having a relatively low melting temperature, such as theone mainly comprising p-hydroxybenzoic acid and 6-hydroxynaphthoic acid,or the one mainly comprising p-hydroxybenzoic acid, terephthalic acidand aliphatic diol.

Polyamide resins are excellent in high strength, high toughness andprocessability, and are widely used for hoses, tubes, pipes, and thelike. On the other hand, those resins, though being excellent generallyin oil resistance, are week against alcohol solvents. Particularly whengasolines containing low grade alcohol are used, oil resistance (gasoholresistance) deteriorates, and volumetric swelling and fuel permeabilityincrease, which causes deterioration of materials such as decrease instrength.

The solvent resistance and gasohol resistance of that polyamide can beimproved by blending the fluorine-containing polymer having a functionalgroup of the present invention with the polyamide and also by applying,as a compatibilizing agent, the fluorine-containing polymer having afunctional group to the blend of the fluorine-containing polymer and thepolyamide.

In that case, the both of hydroxy group and epoxy group (includingglycidyl group) of the present invention can be used as the functionalgroup of the fluorine-containing polymer. Particularly preferable arethe polymers having epoxy group (including glycidyl group) at the end orthe side chain thereof, because epoxy group is considered to have a goodreactivity with the both of carboxyl group and amino group at the end ofa polyamide resin.

When blending two components of the fluorine-containing polymer having afunctional group and the polyamide, various polymers can be selecteddepending on the purpose and uses thereof, and particularly preferableare ETFE, ECTFE, PVDE, VDF copolymer resins and fluorine-containingelastomer, of which respective ends or side chains have a functionalgroup.

Also, when blending three components, that is to say, thefluorine-containing polymer having a functional group of the presentinvention as a compatibilizing agent and a blend of afluorine-containing polymer and polyamide, various combinations can beused. The most preferable are a composition comprising a blend of a ETFE(or ECTFE) and a polyamide and, as a compatibilizing agent, anethylene/tetrafluoroethylene (or ethylene/chlorotrifluoroethylene)copolymer which has epoxy group (including glycidyl group) at the end orside chain thereof, a composition comprising a blend of a PVDF and apolyamide and, as a compatibilizing agent, a fluorine-containing polymerselected from a PVDF and a VDF copolymer, which has epoxy group(including glycidyl group) at the end or side chain thereof, and acomposition comprising a blend of a VDF copolymer and a polyamide resinand a fluorine-containing polymer selected from a PVDF and a VDFcopolymer, which has epoxy group (including glycidyl group) at the endor side chain thereof.

In that case, a content of the fluorine-containing polymer having afunctional group, which is effective for enhancing a dispersibility as acompatibilizing agent, is 0.5 to 30% by weight, preferably 2 to 15% byweight per a total amount of the composition.

As the polyamide resins of the present invention, there can be usednylon 6, nylon 6,6, nylon 11, nylon 12, nylon 610, nylon 46, nylonMCX-A, nylon MXD 6, and the like.

Further, the resin composition of the present invention may containfibrous reinforcements, for exmaple, glass fiber, carbon fiber, ceramicfiber, potassium titanate fiber and aramide fiber, inorganic fillers,for example, calcium carbonate, talc, mica, clay, carbon powder,graphite, and glass beads, and inorganic or organic fillers usuallyused, for example, heat resisting resins such as polyimides, colorantsand flame retarders within ranges not impairing the effect of thepresent invention. A content thereof is usually 1 to 70% by weight perthe composition weight. At that time, there is a case where an effectthereof is enhanced more because of the presence of a non-reactedfunctional group being contained in the resin composition of the presentinvention.

The present invention is explained further concretely by means of thefollowing Reference Examples, Examples and Comparative Examples. It isto be understood that the present invention is not limited to the scope.

The fluorine-containing polymers synthesized in the Reference Examplesand the resin compositions obtained in Examples and Comparative Exampleswere evalulated by the following test methods.

(Test Methods) (1) Measurement of Thermal Resistance of theFluorine-Containing Polymer Having a Functional Group

A temperature was measured at the time when the weight decreased by 1%in nitrogen (30 ml /min.) at heat-up rate of 10° C. /min. by the use ofa heat analyzing unit DT-30 type of Shimazu Corporation.

(2) Izod Impact Test

An Izod notched impact strength was measured in accordance with ASTMD256 by the use of a U-F impact tester of Ueshima Seisakusho Ltd.

(3) Electronmicroscopic Observation

A molded article of a resin composition was frozen and broken in liquidnitrogen, and the section thereof was observed by a scanning typeelectron microscope. Further, a hundred of the fluorine-containingpolymer particles were optionally selected from the microscopicphotograph (150 μm×200 μm), and an average particle size was obtainedtherefrom.

(4) Tension Test

A tensile strength was measured in accordance with ASTM D638 by the useof a Tensilon universal tester of Orientec Corporation and a type 5dumbbell.

(5) Melt Flow Rate

A melt flow rate was measured at a temperature of 250° C. and a load of20 kgf/cm² for 300 seconds of preheating by the use of a flow tester ofShimazu Corporation.

(6) Deflection Temperature Under Load

Measurement was made under the conditions of a load of 18.5 kgf/cm² andthermal up rate of 2° C./min. in N₂ stream by the use of a thermaldistortion tester (No. 148 HD-500-PC type) of Yasuda Seiki SeisakushoLtd.

(7) Solvent Resistance

A volume change was measured by the use of a mixed solvent oftoluene/isooctane/methanol at 40/40/20% by volume respectively inaccordance with JIS-K630 after 70 hr dipping at 100° C.

Reference Example 1

By the method disclosed in Example 3 (1) of JP-B-49327/1986, there wasobtained a white aqueous latex which contained 25% by weight of solidsof 50/20/30% by mole of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene copolymer which wasprovided with iodine at the end thereof by a method with a chaintransfer agent. A part of that latex was frozen, coagulated, rinsed anddried, thus an achromatic transparent elastomer was obtained. Anumber-average molecular weight of that polymer, which was obtained byGPC analysis (solvent: THF, column temperature: 40° C.), was about 140thousands by a conversion with polystyrene, and an iodine content by anelement analysis was 0.22% by weight. Also, thermal resistance of thatpolymer was 401° C.

A 2000 ml four neck flask equipped with an agitator, cooling tube,thermometer and nitrogen blowing tube was charged with 1000 g of thatlatex and 4.2 g of allyl alcohol, and was then heated to 70° C. on awater bath, being agitated under a nitrogen stream at a flow rate ofabout 0.2 ml/min. 10 ml of an aqueous solution, in which 20 mg ofammonium persulfate had been melted, was added in the flask, and areaction was started. After a lapse of seven hours, heating andagitation were stopped for cooling. After having been frozen andcoagulated, the latex was rinsed and dried, and an achromatictransparent elastomer was obtained. Subsequently a 2000 ml four neckflask equipped with an agitator, cooling tube and thermometer wascharged with 250 g of that elastomer and 1 liter of ethyl acetate, andheating and agitation were carried out to melt the polymer. With a flaskinner temperature being kept at 70° C., 200 g of an aqueous solutionhaving 10% by weight of potassium hydroxide was added, and the reactionwas done for seven hours. The reacted solution was poured into a largeamount of methanol to re-precipitate and recover the polymer which wasthen rinsed and dried. A content of iodine at the end thereof was 0.14%by weight by an element analysis, and the epoxidation ratio obtained byan iodine amount having decreased by the epoxidation reaction was 36%.Also, thermal resistance of the polymer was 356° C., and the glasstransition point was -9° C. The concentration of epoxy group containedin that polymer was calculated with a number-average molecular weight,that is, 5 μmol/g.

Reference Example 2

A 1-liter pressure vessel equipped with an agitator was charged with 500g of the latex of the iodine terminated fluorine-containing elastomersynthesized in Reference Example 1, and after substituting the inner gassufficiently with nitrogen gas, the vessel pressure was increased to 0.8MPa by ethylene gas with the vessel temperature being kept at 70° C.under the agitation. By forcedly charging 50 mg of APS, immediately apressure drop started. At the stage where a pressure drop was no longerfound after a lapse of 14 hours, the vessel temperature was lowered toroom temperature, and the remaining pressure was discharged to completethe reaction. After freezing and coagulating of the resulting latex,rinsing and drying were carried out to obtain an achromatic transparentelastomer. In the infrared absorption spectrum of that polymer, therewas recognized a characteristic absorption of CH bond of ethyleneintroduced in the end iodine, at 3024 cm⁻¹.

Then a 1000 ml four neck flask equipped with an agitator, cooling tube,thermometer and nitrogen blowing tube was charged with 68 g of thatelastomer, 3.0 g of dimethyl sulfoxide, 400 g of butyl acetate and 2 gof water, and were heated up to 110° C., being agitated under a nitrogengas stream at a rate of about 0.2 ml/min. After a lapse of five hours,heating and agitation were stopped, and the yellow-colored polymersolution was obtained. That solution was poured into a large amount ofmethanol to recover the polymer. Afterwards rinsing and drying wererepeated in the methanol to obtain light yellowish elastomer. In theinfrared absorption spectrum of that polymer, there was recognized acharacteristic absorption of hydroxy group caused by the end reaction,at 3400 cm⁻¹.

The content of the end iodine by an element analysis was 0.10% byweight, and the hydroxylation ratio obtained by the iodine amount havingdecreased by the hydroxylation reaction was 55%. Also, thermalresistance of that polymer was 453° C., and the glass transition pointwas -9° C. The concentration of hydroxy group contained in that polymerwas calculated by a number-average molecular weight, that is, 8 μmol/g.

Reference Example 3

A 3-liter stainless autoclave equipped with a stainless agitation bladeand a jacket for temperature control was charged with 1425 ml ofdeionized water and 0.75 g of emulsifier (ammonium perfluorooctanoate),and oxygen in a system was substituted with a nitrogen gas three timesto discharge oxygen therefrom. Then the autoclave was charged with 8.1 gof CF₂ ═CFCF₂ CH₂ OH, and 78 g of a vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (3/1/1 of mole ratio)mixture monomer was forcedly charged. By keeping the agitator at 400 rpmand the inner temperature at 40° C., the inner pressure became 1.2 MPa.Then an aqueous ammonium persulfate solution (6 g/25 ml), aqueous sodiumsulfite solution (3.18 g/25 ml), and aqueous ferric sulfate solution(3.66 g/25 ml) were forcedly charged in order with the mixture monomer.During the reaction, the mixture monomer was continuously supplied tokeep the temperature at 40° C., the agitation of 400 rpm and the innerpressure of 1.1 MPa. Also, an ammonium persulfate amounting to a half ofthat supplied at the time of starting the reaction was additionallysupplied four hours later.

When the amount of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (3/1/1, mole ratio)mixture monomer consumption for the reaction had reached 400 g afteraddition of initiators (about 15 hours later), the agitation and supplyof the mixture monomer were stopped immediately, and gases remaining inthe autoclave were discharged until normal pressure was reached, and thereaction completed. The obtained fluorine-containing copolymer wasrinsed and dried under the reduced pressure at 70° C. for 24 hours. Theresulting dried powder was 430 g in total.

An absorption peak reverted to hydroxy group of CF₂ ═CFCF₂ CH₂ OH wasrecognized at 3420 cm⁻¹ of the infrared absorption spectrum of the filmobtained by compression-molding of the dried powder. The elementanalysis and the 19F nuclear magnetic resonance analysis (NMR) indicatethat the fluorine-containing polymer comprised a vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene/CF₂ ═CFCF₂ CH₂ OH(57.4/25.6/16.8/0.2). A number-average molecular weight of that polymer,which was obtained by GPC analysis (solvent: THF, column temperature:40°C.), was about 60 thousands by a conversion with polystyrene. Also,thermal resistance of that polymer was 401° C., and the glass transitionpoint was -18° C . The concentration of the hydroxy group contained inthe polymer is calculated to be 18 μmol/g.

Reference Example 4

A 3-liter stainless autoclave equipped with a stainless agitation bladeand a jacket for temperature control was charged with 1425 ml ofdeionized water and 0.75 g of emulsifier (ammonium perfluorooctanoate),and oxygen in the system was substituted with a nitrogen gas three timesto discharge oxygen therefrom. Then the autoclave was charged with 3 gof CF₂ ═CFCF₂ CH₂ OH, and 78 g of a mixture monomer of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (3/1/1, mole ratio) wasforcedly charged therein. By keeping an agitation at 400 rpm and aninner temperature at 40° C., the inner pressure became 1.2 MPa.Subsequently an aqueous ammonium persulfate solution (6 g/25 ml),aqueous sodium sulfite solution (3.18 g/25 ml), and aqueous ferricsulfate solution (3.66 g/25 ml) were forcedly charged in order with themixture monomer. During the reaction, the temperature was kept at 40° C.and the agitation, at 400 rpm. The mixture monomer was continuouslysupplied to keep the inner pressure at 1.1 MPa. Also, the ammoniumpersulfate was additionally continuously supplied in a total amount of 3g for ten hours from the start of the reaction.

When the amount of the mixture monomer of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (3/1/1, mole ratio),which had been consumed by the reaction after addition of initiators,reached 400 g (after a lapse of about 22 hours), the agitation andsupply of the mixture monomer were immediately stopped, and gasesremaining in the autoclave were discharged until the normal pressure wasreached, and the reaction was completed. The obtainedfluorine-containing copolymer was coagulated and rinsed, and then driedat 70° C. for 24 hours under the normal pressure. The resulting driedpowder was 380 g in total.

The element analysis and ¹ H, ¹⁹ F nuclear magnetic resonance analysis(NMR) indicate that the fluorine-containing polymer comprised avinyliden fluoride/tetrafluoroethylene/hexafluoropropylene/CF₂ ═CFCF₂CH₂ OH (62.8/23.8/13.3/0.08, mole ratio). A number-average molecularweight of the polymer, which was obtained by GPC analysis (solvent:THF,column temperature: 40° C.), was about 210 thousands by a conversionwith polystyrene. Thermal resistance of that polymer was 445° C., andthe glass transition point was -19° C. The concentration of OH groupcontained in the polymer is calculated to be 12 μmol/g.

Reference Example 5

In accordance with the method disclosed in JP-A-12734/1987, a whiteaqueous latex having 21% by weight of solids of a vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene/CF₂ ═CFOCF₂ CF₂ CH₂ l(49.7/19.9/29.8/0.6, mole ratio) copolymer was obtained. Aftercoagulated, that latex was rinsed and dried to obtain an achromatictransparent elastomer. A number-average molecular weight of the polymer,which was measured by GPC analysis (solvent: THF, column temperature:40° C.), was about 140 thousands by a conversion with polystyrene. Theiodine content measured by an element analysis was 0.72% by weight.Also, thermal resistance of that polymer was 403° C.

A 6-liter autoclave made of glass, which was equipped with a glasslining agitation blade and a jacket for temperature control, was chargedwith 3300 g of that latex, and after oxygen in the system wassubstituted with a nitrogen gas three times, the inner pressure wasincreased up to 0.9 Mpa with an ethylene gas with the agitation andinner temperature being kept at 305 rpm and 70° C. respectively.Subsequently an aqueous ammonium persulfate solution (30 mg/2 ml) wasforcedly charged with a nitrogen gas. During the reaction, thetemperature was kept at 70° C., and the agitation, at 305 rpm.

When a pressure drop was no longer found (after a lapse of about 13.5hours), gases remaining in the autoclave were discharged until thenormal pressure was reached, and the reaction was completed. Theobtained fluorine-containing copolymer was coagulated and rinsed, andthen dried at 80° C. for 48 hours under the normal pressure. Thus theachromatic transparent elastomer was obtained. The resulting driedpolymer was 690 g in total.

By ¹ H nuclear magnetic resonance analysis (NMR), it was confirmed thata peak of 4.0 ppm resulting from --CF₂ CH₂ I bond had disappeared andethylene had been added. An element analysis indicates 0.57% by weightof iodine, and a number-average molecular weight of the polymer, whichwas measured by GPC analysis (solvent: THF, column temperature: 40° C.),was about 140 thousands by a conversion with polystyrene. Also, thermalresistance of that polymer was 427° C.

A 1000 ml four neck flask equipped with an agitator, cooling tube,thermometer and nitrogen gas blowing tube was charged with 100 g ofethylene-added iodine-terminated fluorine-containing elastomer, 400 g ofdimethyl sulfoxide (DMSO) and 2 g of water, and was heated to 100° C.,being agitated under bubbling with nitrogen gas blown at a rate of about0.2 ml/min. Five hours later, heating and agitating were stopped, and ayellow-colored polymer was obtained. That polymer was melted in acetoneto obtain a yellow-colored polymer solution. That solution was poured ina large amount of methanol for recovering the polymer which was then,after further rinsing, dried at 100° C. for 24 hours under normalpressure, and a light yellow polymer was obtained.

The iodine content by an element analysis was 0.11% by weight. Thehydroxylation ratio calculated by an iodine amount having decreased bythe hydroxylation reaction was 80.7%. The thermal resistance of thatpolymer was 452° C. The concentration of hydroxy group contained in thatpolymer is calculated by the number-average molecular weight to be 57μmol/g.

EXAMPLE 1

A 60 cm³ Brabender mixer set at 300° C. was filled with 50.4 g ofpolyphenylene sulfide (Tohpren T4 of Tohpren Co., Ltd.), and melting wascarried out for four minutes at 50 rpm. Then 7.6 g of the polymerobtained in Reference Example 1 was added, and then kneaded for sixminutes at 100 rpm. In that csae, the degree of the torque increaseduring kneading was larger than that of Comparative Example 1 asdescribed hereinafter. The obtained composition was compression-moldedat 300° C., and a test piece was made. The test results are shown inTable 1.

EXAMPLES 2, 3 and 4

44.8 G of a polyphenylene sulfide resin was kneaded and molded in thesame manner as in Example 1, with the use of 15.2 g each of the polymersobtained in Reference Examples 1, 2 and 3, and a test piece was made.The test results are shown in Table 1.

EXAMPLE 5

44.8 G of a polyphenylene sulfide resin, 3.2 g of the polymer obtainedin Reference Example 1 and 15.2 g of a fluorine-containing elastomer(Daiel G701 of Daikin Industries, Ltd.) comprising a vinylidenefluoride/hexafluoropropylene copolymer were kneaded and molded in thesame manner as in Example 1, and a test piece was made. The test resultsare shown in Table 1.

Comparative Example 1

44.8 G of a polyphenylene sulfide resin and 15.2 g of afluorine-containing elastomer (Daiel G701 of Daikin Industries, Ltd.)comprising a vinylidene fluoride/hexafluoropropylene copolymer werekneaded and molded in the same manner as in Example 1, and a test piecewas made. The test results are shown in Table 1.

Comparative Example 2

A 60 cm³ Brabender mixer set at 300° C. was filled with 60 g of apolyphenylene sulfide resin, and melting was carried out at 500 rpm forfour minutes, and further melting was done at 100 rpm for six minutes.Then a test piece was made in the same manner as in Example 1. The testresults are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                  Examples        Comparative Examples                                          1  2  3   4 5   1    2                                          __________________________________________________________________________    Components (% by weight)                                                      Fluorine-containing polymer (a)                                               having a functional group                                                     Reference Example 1                                                                         4.7                                                                              9  --  --                                                                              1.8 --   --                                         Reference Example 2                                                                         -- -- 13.8                                                                              --                                                                              --  --   --                                         Reference Example 3                                                                         -- -- --  25                                                                              --  --   --                                         Thermoplastic resin (b)                                                                     87 75 75  75                                                                              71  75   100                                        Others        8.3.sup.(1)                                                                      16.sup.(1)                                                                       11.2.sup.(1)                                                                      --                                                                              27.2.sup.(2)                                                                      25.sup.(3)                                                                         --                                         Properties of molded article                                                  Izod impact strength (kgcm/cm)                                                              1.7                                                                              2.1                                                                              4.2 4.5                                                                             1.7 1.5  1.4                                        Average dispersion particle                                                                 3  4  1   2 5   9    --                                         size (μm)                                                                  __________________________________________________________________________     .sup.(1) Vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene          copolymer (equal to nonreacted portion of Reference Examples 1 and 2)         .sup.(2) A mixture of a vinylidene fluoride/hexafluoropropylene copolymer     (Daiel G701 of Daikin Industries, Ltd.) and a nonreacted portion of           Reference Example 1                                                           .sup.(3) Daiel G 701 alone of (2) above                                  

FIGS. 1, 2, 3 and 4 are microscopic photographs (×500) respectivelyshowing the cut surfaces of the molded articles obtained in Example 2and 3 and Comparative Examples 1 and 2.

As is clear from FIGS. 1 to 4, a dispersibility of a fluorine-containingelastomer of a blend of the fluorine-containing elastomer (ReferenceExamples 1 and 2), in which a functional group is introduced, with apolyphenylene sulfide (Example 2-FIG. 1, and Example 3-FIG. 2respectively) is better than the case (Comparative Example-FIG. 3) wherethe conventional fluorine-containing elastomer is blended. Thus it canbe observed that the improvement of mechanical property (Izod impactstrength) are effectively done.

EXAMPLE 6

A 60 cm³ Brabender mixer set at 200° C. was filled with 8.3 g of liquidcrystal copolyester (Novaculate E310 of Mitsubishi Kasei Corp.) whichwas melted at 10 rpm for 1.5 minutes. Then 73.8 g of the polymerobtained in Reference Example 3 was added at 50 rpm, and was kneaded at100 rpm for five minutes. The obtained composition wascompression-molded at 200° C., and a test piece was made. The testresults are shown in Table 2.

EXAMPLE 7

8.3 G of liquid crystal copolyester (Novaculate E310) was kneaded with73.8 g of the polymer obtained in Reference Example 4 and molded in thesame manner as in Example 6, and a test piece was made. The test resultsare shown in Table 2.

EXAMPLE 8

8.3 G of liquid crystal copolyester (Novaculate E310) was kneaded with73.9 g of the polymer obtained in Reference Example 5 and molded in thesame manner as in Example 6, and a test piece was made. The test resultsare shown in Table 2.

Comparative Example 3

420 G of a fluorine-containing polymer having no functional group wasobtained in the same manner as in Reference Example 3 except that CF₂═CFCF₂ CH₂ OH was not used.

The components of the fluorine-containing polymer, which was obtained byan element analysis and ¹ H, ¹⁹ F nuclear magnetic resonance analysis(NMR), was vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene(61.3/18.9/19.8, mole ratio). A number-average molecular weight of thatpolymer was calculated by GPC analysis (solvent: THF, columntemperature: 40° C.) to be about 210 thousands by a conversion withpolystyrene. The thermal resistance of that polymer was 456° C., and theglass transition point was -17° C.

73.8 G of that fluorine-containing polymer having no functional groupwas kneaded with 8.3 g of liquid crystal copolyester (Novaculate E310)and molded, and then a test piece was made in the same manner as inExample 6. The test results are shown in Table 2.

Comparative Example 4

73.9 G of the fluorine-containing elastomer which was prepared bycoagulating, rinsing and drying a latex synthesized in Reference Example5 prior to addition of ethylene thereto, was kneaded with 8.2 g ofliquid crystal copolyester (Novaculate E310) and molded, and then a testpiece was made in the same manner as in Example 6. The test results areshown in Table 2.

                  TABLE 2                                                         ______________________________________                                                                   Comparative                                                       Examples    Examples                                                          6    7      8       3    4                                     ______________________________________                                        Components (% by weight)                                                      Fluorine-containing polymer (a)                                               having a functional group                                                     Reference Example 3                                                                            90     --     --    --   --                                  Reference Example 4                                                                            --     90     --    --   --                                  Reference Example 5                                                                            --     --     72.6  --   --                                  Thermoplastic resin (b)                                                                        10     10     10    10   10                                  Others           --     --     17.4.sup.(1)                                                                        90.sup.(2)                                                                         90.sup.(3)                          Properties of molded article                                                  Maximum tensile strength                                                                       186    146    29.7  9.0  5.6                                 (kgf/cm.sup.2)                                                                Melt flow rate (g/10 min)                                                                      74.4   59.3   7.3   108  119                                 ______________________________________                                         .sup.(1) Vinylidene                                                           fluoride/tetrafluoroethylene/hexafluoropropylene/CF.sub.2 ═CFOCF.sub.     CF.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 I copolymer (equal to nonreacted          portion of Reference Example 7)                                               .sup.(2) A mixture of vinylidene                                              fluoride/tetrafluoroethylene/hexafluoropropylene copolymer (synthesized i     Comparative Example 3) and nonreacted portion                                 .sup.(3) Vinylidene                                                           fluoride/tetrafluoroethylene/hexafluoropropylene/CF.sub.2 ═CFOCF.sub.     CF.sub.2 CH.sub.2 I copolymer (obtained by coagulating, rinsing and dryin     a latex before addition of ethylene, which was synthesized in Example 5) 

FIG. 5 shows a stress-strain curve obtained in Reference Examples 6, 7,8 and Comparative Examples 3 and 4.

As is clear from Table 2 and FIG. 5, a blend (same as those of ReferenceExamples 6, 7 and 8) of a fluorine-containing elastomer (synthesized inReference Examples 3, 4 and 5), in which a functional group wasintroduced, and a liquid crystal copolyester shows a high stress againstthe elongation and has crosslinking rubber like physical properties.Also the blend of the functional group-introduced fluorine-containingelastomer and the liquid crystal copolyester shows a high temperatureflowability, and therefore has thermoplastic elastomeric properties.Because a blend (same as those of Comparative Examples 3 and 4) with afluorine-containing elastomer having no functional group is a mere blendof a non-vulcanized rubber and a liquid crystal copolyester, andtherefore has a flowability at high temperature but shows only a lowstress against an elongation.

EXAMPLE 9

8.0 G of a polycarbonate (Panlite L1225WP available from TeijinChemicals Ltd.) and 72.4 g of the polymer obtained in Reference Example4 were kneaded in the Brabender mixer set at 285° C. in the same manneras in Example 6. The obtained composition was compression-molded at 285°C., and a test piece was made. The test results are shown in Table 3.

EXAMPLE 10

8.1 G of polybutyrene terephthalate (Valox 310 available from GEPlastics Japan Ltd.) and 73.3 g of the polymer obtained in ReferenceExample 4 were kneaded in the Brabender mixer set at 240° C. in the samemanner as in Example 6. The obtained composition was compression-moldedat 240° C., and a test piece was made. The test results are shown inTable 3.

Comparative Example 5

Kneading and molding were carried out by the use of afluorine-containing polymer having no functional group as shown inComparative Example 3 in the same manner as in Example 9, and a testpiece was made. The test results are shown in Table 3.

Comparative Example 6

Kneading and molding were carried out by the use of afluorine-containing polymer having no functional group as shown inCompartive Example 3 in the same manner as in Example 10, and a testpiece was obtained. The test results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                   Examples    Comparative Examples                                              9      10       5        6                                         ______________________________________                                        Components                                                                    (% by weight)                                                                 Fluorine-containing                                                                        90       90       --     --                                      elastomer (a) having a                                                        functional group (Syn-                                                        thesized in Reference                                                         Example 4)                                                                    Thermoplastic resin (b)                                                       Polycarbonate                                                                              10       --       10     --                                      Polybutyrene tere-                                                                         10       --       10     --                                      phthalate                                                                     Fluorine-containing ela-                                                                   --       --       90     90                                      stomer (4) having no                                                          functional group                                                              Properties                                                                    of molded article                                                             Maximum tensile                                                                            163      119      10.7   10.4                                    strength (kgf/cm.sup.2)                                                       Elongation at break (%)                                                                    695      647      --     --                                      Melt flow rate (g/10 min)                                                                  4.9      130      110    102                                                  (Measured                                                                              (Measured                                                                              (Measured                                                                            (Measured                                            at       at       at     at                                                   300° C.)                                                                        290° C.)                                                                        300° C.)                                                                      290° C.)                         ______________________________________                                         .sup.(1) Vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene          copolymer (synthesized in Comparative Example 3)                         

When blending a fluorine-containing elastomer (synthesized in ReferenceExample 4) with a polycarbonate (Example 9) and also polybutyreneterephthalate (Example 10), the resulting blend shows a strong stressagainst an elongation, and further shows a high temperature flowability,which represents thermoplastic elastomeric properties. Contrary to that,the compositions of Comparative Examples 5 and 6 show only a low stressagainst an elongation like non-vulcanized rubbers.

EXAMPLE 11

There were uniformly blended a PVDF (Neoflon VDF VP-800 available fromDaikin Industries, Ltd.), a liquid crystal polyester (VectraA950-non-reinforced available from Polyplastic Co., Ltd.) and afluorine-containing polymer having a functional group as shown inReference Example 4, in a weight ratio shown in Table 4. Then kneadingand extruding were carried out at 280° to 300° C. by a twin screwextruder to make pellets. By the use of those pelletes, test pieces weremade at a cylinder temperature of 240° to 290° C. and a mold temperatureof 50° C. by an injection molding machine. The test results are shown inTable 4.

Comparative Example 7

By the use of a PVDF (same as that of Example 11) and a liquid crystalpolyester (same as that of Example 11), kneading and extruding werecarried out in the same manner as in Example 11, and a test piece wasmade by an injection molding. The test results are shown in Table 4.

EXAMPLE 8

The pellets of the PVDF (same as that of Example 11) wereinjection-molded under the same conditions as in Example 11, and a testpiece was obtained. The test results are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                                                 Comparative                                                           Example Examples                                                              11      7      8                                             ______________________________________                                        Components (% by weight)                                                      Fluorine-containing polymer (a)                                                                   3        --     --                                        having a functional group                                                     Reference Example 4                                                           Thermoplastic resin (b)                                                                          20        20     --                                        Liquid crystal polyester                                                      Others             77        80     100                                       PVDF resin                                                                    Deflection temperature                                                                           146       130    101                                       under load (°C.)                                                       ______________________________________                                    

It is known from Table 4 that the deflection temperature under load canbe further improved to a large extent by adding the fluorine-containingpolymer having a functional group (the one synthesized in ReferenceExample 4) when blending the fluorine-containing resin and the liquidcrystal polyester, as compared with the blend (Comparative Example 7) ofonly a fluorine-containing resin and a liquid crystal polymer.

EXAMPLE 12

A 60 cm³ Brabender mixer set at 190° C. was charged with 40.4 g ofpolyamide 12 (Rilsan AMNφ available from Toray Industries, Inc.) whichwas then melted at 10 rpm for 1.5 minutes. 10.1 g of the polymerobtained in Reference Example 1 was added at 50 rpm and was kneaded at80 rpm for 7 minutes. The obtained composition was compression-molded at200° C., and a test piece was made. The test results are shown in Table5.

EXAMPLE 13

A 60 cm³ Brabender mixer set at 190° C. was charged with 40.2 g ofpolyamide 12 (same as that of Example 12) and 13.4 g of PVdF (same asthat of Example 11), and melting was carried out at 10 rpm for twominutes. 2.5 G of the polymer obtained in Reference Example 1 was addedat 50 rpm, and kneaded at 80 rpm for seven minutes. The obtainedcomposition was compression-molded at 200° C., and a test piece wasmade. The test results are shown in Table 5.

Comparative Example 9

Kneading and molding were carried out in the same manner as in Example12 except that the fluorine-containing elastomer (Daiel G902 availablefrom Daikin Industries, Ltd.) was used instead of thefluorine-containing polymer having functional group obtained inReference Example 1, and a test piece was made. The test results areshown in Table 5.

Comparative Example 10

A 60 cm³ Brabender mixer set at 190° C. was charged with 40.1 g ofpolyamide 12 (same as that of Example 12) and 10.0 g of PVdF (same asthat of Example 11), and kneading was carried out at 10 rpm for twominutes and further at 80 rpm for seven minutes. The obtainedcomposition was compression-molded at 200° C., and a test piece wasmade. The test results are shown in Table 5.

Comparative Example 11

The pellets of polyamide 12 (same as that of Example 12) wascompression-molded, and a test piece was made. The test results areshown in Table 5.

                  TABLE 5                                                         ______________________________________                                                       Examples                                                                              Comparative Examples                                                  12   13     9      10    11                                    ______________________________________                                        Components (% by weight)                                                      Fluorine-containing elastomer (a)                                                              20     5      --   --    --                                  having a functional group                                                     (Synthesized in Reference                                                     Example 1)                                                                    Thermoplastic resin (b)                                                                        80     80     80   80    100                                 Polyamide                                                                     Others                                                                        PVDF             --     15     --   20    --                                  Fluorine-containing elastomer (1)                                                              --     --     20   --    --                                  Solvent resistance test                                                                        18     16     27   23    30                                  Volume change (%)                                                             Izod impact strength (kgcm/cm)                                                                 3.8    --     2.0  --    1.8                                 Average dispersion particle size                                                               1      --     6    --    --                                  (μm)                                                                       ______________________________________                                         .sup.(1) Vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene          copolymer (Daiel G902 of Daikin Industries, Ltd.)                        

As is clear from Table 5, the blend (same as that of Example 12) of afluorine-containing polymer having a functional group and a polyamideand the blend (same as that of Example 13) of a fluorine-containingpolymer having a functional group and a mixture of a PVDF and polyamideshows a good effect on the improvement in chemical resistance (gasoholresistance).

FIGS. 6 and 7 show microscopic photographs (×5000) of cut surfaces ofthe molded articles obtained in Example 12 and Comparative Example 9,respectively.

As is clear by comparing FIG. 6 with 7, the blend (same as that ofExample 12) of a fluorine-containing polymer (synthesized in ReferenceExample 1) having a functional group and a polyamide shows a gooddispersibility of the fluorine-containing polymer as compared with theblend (same as that of Comparative Example 9) of a fluorine-containingpolymer having no functional group and a polyamide. It is observed thatmechanical properties (Izod impact strength) are effectively carriedout.

By introducing a functional group in a fluorine-containing polymer, aninterfacial affinity of the resin composition of the present inventionis improved, and the resin composition is presented as the materialssuitable for various functional parts, having excellent mechanicalproperties and moldability of the thermoplastic resin together withexcellent chemical resistance and impact resitance of thefluorine-containing polymer.

INDUSTRIAL APPLICABILITY

In the present invention, the fluorine-containing polymer (a) having afunctional group is blended with the thermoplastic resin (b) of acrystalline melting point or glass transition temperature of not lessthan 150° C. As thermoplastic resins, there are, for example,polyacetals, polyamides, polycarbonates, polyphenylene ethers, aromaticpolyesters, aromatic polyesteramides, aromatic azomethines, polyallylenesulfides, polysulphones and polyether sulfones, polyketones andpolyether ketones, polyetherimides, polyamide imides,polymethylpentenes, polyether nitrites and also polymer alloy mainlycomprising those resins. Among those, preferable for the presentinvention are such resins, for which general modifiers for impactresistance and chemical resistance cannot be used because ofinsufficient thermal resistance as a melting and kneading temperature isnot less than 200° C. As such resins, there are aromatic polyesters,polyamides, polyamide imides, polyallylene sulfides, polyketones,polyether nitrites, polycarbonates, polyphenylene ethers, polysulphones,polyether imides, and polyimides.

What is claimed is:
 1. A thermoplastic resin composition which comprisesa blend obtained by blending 0.1 to 99% by weight of (a) afluorine-containing polymer having a functional group and anumber-average molecular weight of 2000 to 1000000 and 1 to 99% byweight of (b) a heat resisting thermoplastic aromatic polyester having acrystalline melting point or glass transition temperature of not lessthan 150° C.; said fluorine-containing polymer (a) having the functionalgroup is at least one selected from fluorine-containing polymers havingfunctional groups, in which a concentration of the functional groups ata main chain end portion and side chain portion is 2 to 2000μ mol/g perthe total weight of the fluorine-containing polymer, and represented bythe formula (I),

    A.sup.1 --(X)--(Y)--A.sup.2                                (I)

wherein X is a structural unit of the formula --(CH₂ CX¹ X²)-- (whereinX¹ and X² are the same or different, and each is hydrogen atom, fluorineatom, --(CH₂)_(p) --(O)_(q) --R--B¹ (R is a dihydric hydrocarbon grouphaving carbon atoms of 1 to 20 or dihydric fluorine-substituted organicgroup having carbon atoms of 1 to 20, B¹ is hydrogen atom, fluorineatom, hydroxy group or epoxy group, p is 0 or 1 and q is 0 or 1),--OCO--R--B¹ (R and B¹ are the same as above) or --COO--R--B¹ (R and B¹are the same as above)); Y is a structural unit of the formula --(CF₂CY¹ Y²)-- (wherein Y¹ and Y² are the same or different, and each ishydrogen atom, fluorine atom, chlorine atom, --(CF₂)_(r) --(O)_(s)--(R_(f))_(t) --CH₂)_(u) --B² (R_(f) is a dihydric fluorine-substitutedorganic group having carbon atoms of 1 to 14, B² is hydrogen atom,halogen atom, hydroxy group, epoxy group or glycidyloxy group, r is 0 or1, s is 0 or 1, t is 0 or 1, and u is an integer of 1 to 3) or--(CF_(z))_(v) --B³ (B³ is hydrogen atom, fluorine atom or chlorineatom, and v is an integer of 1 to 10)); both A¹ and A² are end portionsof a main chain; provided that each of X and Y may comprise two or morestructural units; Y may not be present when X has the structural unitderived from CH₂ ═CHF, CH₂ ═CF₂ or fluoroalkyl-α-substituted acrylate(substituent is hydrogen atom, fluorine atom or methyl); X may not bepresent when Y has the structural unit derived from CH₂ ═CF₂ or CH₂═CHCl; at least one of A¹ and A² contains hydroxy group, epoxy group orglycidyl group when both of X and Y do not contain hydroxy group, epoxygroup or glycidyl group; said resin composition contains only thefluorine-containing polymer represented by the formula (I) as thefluorine-containing polymer having functional group.
 2. The compositionof claim 1, wherein the aromatic polyester is a liquid crystal polyesterhaving an anisotropy on melting.
 3. A thermoplastic resin compositionwhich comprises a blend obtained by blending (a) a fluorine-containingelastomer having hydroxy group and a number-average molecular weight of2000 to 1000000 and (b) a heat resisting thermoplastic liquid crystalpolyester having a crystalline melting point or glass transitiontemperature of not less than 150° in a weight ratio of (a)/(b) of 50 to99.9/0.1 to 50;said fluorine-containing elastomer (a) has aconcentration of the hydroxy group at a main chain end portion and sidechain portion of 2 to 20000 μmol/g per the total weight of thefluorine-containing elastomer, and represented by the formula (I),

    A.sup.1 --(X)--(Y)--A.sup.2                                (I)

wherein X is a structural unit of the formula --(CH₂ CX¹ X²)-- (whereinX¹ and X² are the same or different, and each is hydrogen atom, fluorineatom, --(CH₂)_(p) --(O)_(q) --R--B¹ (R is a dihydric hydrocarbon grouphaving carbon atoms of 1 to 20 or dihydric fluorine-substituted organicgroup having carbon atoms of 1 to 20, B¹ is hydrogen atom, fluorineatom, hydroxy group or epoxy group, p is 0 or 1 and q is 0 or 1),--OCO--R--B¹ (R and B¹ are the same as above) or --COO--R--B¹ (R and B¹are the same as above)); Y is a structural unit of the formula --(CF₂CY¹ Y²)-- (wherein Y¹ and Y² are the same or different, and each ishydrogen atom, fluorine atom, chlorine atom, --(CF₂)_(r) --(O)_(s)--(R_(f))_(t) --(CH₂)_(u) --B² (R_(f) is a dihydric fluorine-substitutedorganic group having carbon atoms of 1 to 14, B² is hydrogen atom,halogen atom, hydroxy group, epoxy group or glycidyloxy group, r is 0 or1, s is 0 or 1, t is 0 or 1, and u is an integer of 1 to 3) or--CF₂)_(v) --B³ (B³ is hydrogen atom, fluorine atom or chlorine atom,and v is an integer of 1 to 10)); both A¹ and A² are end portions of amain chain; provided that each of X and Y may comprise two or morestructural units; Y may not be present when X has the structural unitderived from CH₂ ═CHF, CH₂ ═CF₂ or fluoroalkyl-α-substituted acrylate(substituent is hydrogen atom, fluorine atom or methyl); X may not bepresent when Y has the structural unit derived from CF₂ ═CF₂ or CF₂═CHCl; at least one of A¹ and A² contains hydroxy group when both of Xand Y do not contain hydroxy group; said liquid crystal polyester (b)has an anisotropy on melting.